US5023393A - Process for upgrading methane to higher hydrocarbons - Google Patents

Process for upgrading methane to higher hydrocarbons Download PDF

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US5023393A
US5023393A US07454534 US45453489A US5023393A US 5023393 A US5023393 A US 5023393A US 07454534 US07454534 US 07454534 US 45453489 A US45453489 A US 45453489A US 5023393 A US5023393 A US 5023393A
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methane
catalyst
oxygen
process
mixture
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Expired - Fee Related
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US07454534
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Scott Han
Robert E. Palermo
Judith A. Pearson
Dennis E. Walsh
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ExxonMobil Oil Corp
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ExxonMobil Oil Corp
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • C07C2/84Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • C07C2529/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/46Iron group metals or copper
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00Chemistry of hydrocarbon compounds
    • Y10S585/929Special chemical considerations
    • Y10S585/943Synthesis from methane or inorganic carbon source, e.g. coal

Abstract

There is provided a process for the direct partial oxidation of methane with oxygen, whereby organic compounds comprising higher hydrocarbons are produced. The catalyst used in this reaction is an NiZSM-5 catalyst. This catalyst may be prepared by ion exchanging or impregnating a ZSM-5 catalyst with a suitable nickel salt such as nickel nitrate.

Description

BACKGROUND

There is provided a process for the direct partial oxidation of methane with oxygen, whereby organic compounds comprising liquid hydrocarbons are produced. The catalyst used in this reaction is an NiZSM-5 catalyst.

Natural gas is an abundant fossil fuel resource. Recent estimates places worldwide natural gas reserves at about 35×1014 standard cubic feet, corresponding to the energy equivalent of about 637 billion barrels of oil.

The composition of natural gas at the wellhead varies but the major hydrocarbon present is methane. For example the methane content of natural gas may vary within the range of from about 40 to 95 vol. %. Other constituents of natural gas may include ethane, propane, butanes, pentane (and heavier hydrocarbons), hydrogen sulfide, carbon dioxide, helium and nitrogen.

Natural gas is classified as dry or wet depending upon the amount of condensable hydrocarbons contained in it. Condensable hydrocarbons generally comprise C3 + hydrocarbons although some ethane may be included. Gas conditioning is required to alter the coxposition of wellhead gas, processing facilities usually being located in or near the production fields. Conventional processing of wellhead natural gas yields processed natural gas containing at least a major amount of methane.

Processed natural gas, consisting essentially of methane, (typically 85-95 volume percent) may be directly used as clean burning gaseous fuel for industrial heat and power plants, for production of electricity, and to fire kilns in the cement and steel industries. It is also useful as a chemicals feedstock, but large-scale use for this purpose is largely limited to conversion to synthesis gas which in turn is used for the manufacture of methanol and ammonia. It is notable that for the foregoing uses no significant refining is required except for those instances in which the wellhead-produced gas is sour, i.e., it contains excessive amounts of hydrogen sulfide. Natural gas, however, has essentially no value as a portable fuel at the present time. In liquid form, it has a density of 0.415 and a boiling point of minus 162° C. Thus, it is not readily adaptable to transport as a liquid except for marine transport in very large tanks with a low surface to volume ratio, in which unique instance the cargo itself acts as refrigerant, and the volatilized methane serves as fuel to power the transport vessel. Large-scale use of natural gas often requires a sophisticated and extensive pipeline system.

A significant portion of the known natural gas reserves is associated with fields found in remote, difficulty accessible regions. For many of these remote fields, pipelining to bring the gas to potential users is not economically feasible.

Indirectly converting methane to methanol by steam-reforming to produce synthesis gas as a first step, followed by catalytic synthesis of methanol is a well-known process. Aside from the technical complexity and the high cost of this two-step, indirect synthesis, the methanol product has a very limited market and does not appear to offer a practical way to utilize natural gas from remote fields. The Mobil Oil Process, developed in the last decade provides an effective means for catalytically converting methanol to gasoline, e.g. as described in U.S. Pat. No. 3,894,107 to Butter et al. Although the market for gasoline is huge compared with the market for methanol, and although this process is currently used in New Zealand, it is complex and its viability appears to be limited to situations in which the cost for supplying an alternate source of gasoline is exceptionally high. There evidently remains a need for other ways to convert natural gas to higher valued and/or more readily transportable products.

A reaction which has been extensively studied for many years is the direct partial oxidation of methane to methanol. This route, involving essentially the reaction of methane and gaseous oxygen according to the simple equation

CH.sub.4 +1/2O.sub.2 →CH.sub.3 OH

could theoretically produce methanol with no by-product. The homogeneous reaction of methane with oxygen to produce methanol occurs most favorably under high pressure (10 to 200 atm.), moderate temperatures, (350°-500° C.), and at relatively low oxygen concentration. Oxidation to formaldehyde and deep oxidation reactions are minimized under these conditions. The mechanism of methanol formation is believed to involve the methylperoxy radical (CH3 OO.) which abstracts hydrogen from methane. Unfortunately, the per pass yields have been limited. This limited yield has been rationalized as resulting from the low reactivity of the C--H bonds in methane vis-a-vis the higher reactivity of the primary oxygenated product, methanol, which results in selective formation of the deep oxidation products CO and CO2 when attempts are made to increase conversion.

U.S. Pat. No. 4,618,732 to Gesser et al. describes an improved homogeneous process for converting natural gas to methanol. The alleged high selectivity for methanol is ascribed by the inventors to careful premixing of methane and oxygen and to eliminating reactor wall effects by use of glass-lined reactors.

SUMMARY

There is provided a process for synthesizing a mixture of organic compounds comprising higher hydrocarbons including C5 + liquid hydrocarbons by the direct partial oxidation of methane, said process comprising the steps of:

(i) contacting a mixture methane and oxygen with an NiZSM-5 catalyst under sufficient conversion conditions; and

(ii) recovering said mixture of organic compounds comprising higher hydrocarbons.

It will be understood that the expression, higher hydrocarbons, as used herein, means hydrocarbons which have more carbon atoms (i.e. at least 2 carbon atoms) than methane. It will be further understood that the expression, C5 + liquid hydrocarbons, as used herein, means liquid hydrocarbons which have at least 5 carbon atoms.

EMBODIMENTS

The NiZSM-5 catalyst comprises an intimate mixture of Ni and ZSM-5 in a catalytically active form. This catalyst may be prepared by ion exchanging or impregnating ZSM-5 with a suitable nickel salt. This ion exchange or impregnation may take place using either a bound or unbound (i.e., binder free) form of ZSM-5. An example of a bound form of ZSM-5 is an extrudate of ZSM-5 and an alumina binder.

The nickel salt which is ion exchanged or impregnated with ZSM-5 may be a salt which is capable of being converted to nickel oxide upon calcination, especially in the presence of oxygen. An example of such a nickel salt is nickel nitrate.

In the practice of the present invention, it is preferred to use a dual flow system, i.e., a system in which the natural gas and the oxygen or air are kept separate until mixed just prior to being introduced into the reactor. However, if desired, the oxygen and natural gas may be premixed and stored together prior to the reaction. The preferred dual flow system minimizes the risk of fire or explosion. In the dual flow system, the amount of oxygen flow may be controlled so as to prepare a reaction mixture that contains 2 to 20 percent by volume, more preferably 3 to 15 percent of oxygen. Air may be used instead of oxygen without affecting the reaction.

The temperature in the reaction zone may be from about 300° C. to 500° C., and preferably about 350° C. to 475° C. In the preferred mode of operation, the reactor temperature is increased until substantially all of the oxygen is consumed by the reaction, i.e., greater than about 90 percent 02 consumption, and then it is held at about that temperature until further adjustment is required.

The gas hourly space velocity (GHSV) on zeolite may be within the range of about 100 to 100,000 hr -1, preferably about 1,000 to 10,000 hr -1, and most preferably about 2,000 to 8,000 hr -1.

COMPARATIVE EXAMPLE A

An (H)ZSM-5 catalyst having a silica to alumina ratio of 70:1 was mixed with alumina (65% zeolite, 35% binder) and formed into extrudate. The extrudate, ground to 20-40 mesh, (8.0 cc) was mixed with an equal volume of sand and loaded into the reactor's 9/16 inch I.D. pyrex glass liner.

Feed mixtures were prepared from ultra high purity methane and C.P. grade oxygen supplied by Matheson, and the feed was passed over (H)ZSM-5 catalyst. Reaction conditions and the results of the experiments are included in Table I.

COMPARATIVE EXAMPLE B

PtZSM-5 was prepared by ion-exchanging 10 g of the Comparative Example A catalyst with 2.7 g of Pt (NH3)2 (NO3)2 in 200 g H2 O for 24 h at 25° C. The resultant catalyst was washed with water, dried and air-calcined.

This PtZSM-5 catalyst was contacted with a mixture of methane and oxygen in the manner described in Comparative Example A. Reaction conditions and results are included in Table I.

COMPARATIVE EXAMPLE C

CrZSM-5 was prepared by ion-exchanging 15 g of the Comparative Example A catalyst with 4.2 g Cr(NO 3)3.9H2 O in 200 g H2 O for 24 h at 25° C. The resultant catalyst was washed with water, dried and air-calcined.

This CrZSM-5 catalyst was contacted with a mixture of methane and oxygen in the manner described in Comparative Example A. Reaction conditions and results are included in Table I.

EXAMPLE 1

NiZSM-5 was prepared by ion-exchanging 15 g of the Comparative Example A catalyst with 3.0 g Ni(NO3)2.6H2 O in 200 g H2 O for 20 h at 25° C. The resultant catalyst was washed with water, dried and air-calcined.

This NiZSM-5 catalyst was contacted with a mixture of methane and oxygen in the manner described in Comparative Example A. Reaction conditions and results are included in Table I.

EXAMPLE 2

The catalyst loading used in this Example was the same used in Example 1. This catalyst loading was contacted with mixture of methane and oxygen and product collection began after 8 hours time on stream. Reaction conditions and results are included in Table I.

                                  TABLE 1__________________________________________________________________________Catalytic Data and ResultsExample orComparative Example         1    2    A    B    C__________________________________________________________________________Catalyst      NiZSM-5              NiZSM-5                   HZSM-5                        PtZSM-5                             CrZSM-5Time on Stream         fresh              8 hrs.                   fresh                        fresh                             freshPressure, psig         960  960  960  960  960Temp., °C.         465  465  450  450  440GHSV (zeolite), hr .sup.-1         4600 4600 4600 4600 4600% O.sub.2 in feed         7.3  7.3  6.9  7.0  6.8CH.sub.4, conv., %         5.2  5.7  5.2  4.7  5.2Selectivities, %CO.sub.x      83.8 84.0 83.3 97.2 99.2CH.sub.3 OH   6.3  4.5  16.7 1.8  0.8Other aq. phase oxygenates         0.6  1.0  --   --   --C.sub.2 -C.sub.4         5.0  4.5  --   1.0  --C.sub.5 +     4.3  6.0  --   --   --__________________________________________________________________________

As the data in Table 1 clearly show, addition of Ni to the ZSM-5 catalyst improved the C2 -C4 and C5 + selectivities from methane at similar conversions. C5 + liquids are not produced from methane/oxygen feeds over unmodified ZSM-5, CrZSM-5 or PtZSM-5 under similar conditions.

Claims (2)

We claim:
1. A process for synthesizing a mixture of organic compounds comprising higher hydrocarbons including C5 + liquid hydrocarbons by the direct partial oxidation of methane, said process comprising the steps of:
(i) contacting a mixture of methane and oxygen with a NiZSM-5 catalyst under sufficient conversion conditions including a temperature of from about 350° C. to about 475° C. and a pressure of from about 150 psig to about 3000 psig; and
(ii) recovering said mixture of organic compounds comprising higher hydrocarbons.
2. A process according to claim 1, wherein said mixture of methane and oxygen contains from about 3 to about 20 percent by volume of 02.
US07454534 1989-12-21 1989-12-21 Process for upgrading methane to higher hydrocarbons Expired - Fee Related US5023393A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2061598A (en) * 1934-04-26 1936-11-24 Harold M Smith Process for producing ethylene
US4670619A (en) * 1984-04-16 1987-06-02 Atlantic Richfield Company Methane conversion process
US4831204A (en) * 1987-12-16 1989-05-16 Mobile Oil Corporation Production of gasoline from light olefins with FCC gas plant improvement by olefin upgrading
US4831205A (en) * 1987-12-16 1989-05-16 Mobil Oil Corporation Catalytic conversion of light olefinic feedstocks in a FCC plant
US4849571A (en) * 1988-05-20 1989-07-18 Atlantic Richfield Company Hydrocarbon production
US4851602A (en) * 1988-04-11 1989-07-25 Mobil Oil Corporation Alkanes and alkenes conversion to high octane gasoline
US4879424A (en) * 1988-09-19 1989-11-07 Mobil Oil Corporation Conversion of alkanes to gasoline

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2061598A (en) * 1934-04-26 1936-11-24 Harold M Smith Process for producing ethylene
US4670619A (en) * 1984-04-16 1987-06-02 Atlantic Richfield Company Methane conversion process
US4831204A (en) * 1987-12-16 1989-05-16 Mobile Oil Corporation Production of gasoline from light olefins with FCC gas plant improvement by olefin upgrading
US4831205A (en) * 1987-12-16 1989-05-16 Mobil Oil Corporation Catalytic conversion of light olefinic feedstocks in a FCC plant
US4851602A (en) * 1988-04-11 1989-07-25 Mobil Oil Corporation Alkanes and alkenes conversion to high octane gasoline
US4849571A (en) * 1988-05-20 1989-07-18 Atlantic Richfield Company Hydrocarbon production
US4879424A (en) * 1988-09-19 1989-11-07 Mobil Oil Corporation Conversion of alkanes to gasoline

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Owner name: MOBIL OIL CORPORATION, A CORP. OF NY, NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:HAN, SCOTT;PALERMO, ROBERT E.;PEARSON, JUDY A.;AND OTHERS;REEL/FRAME:005204/0805

Effective date: 19891205

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Effective date: 19950614